CN109200772A - The processing method of tail gas during butane cis-butenedioic anhydride - Google Patents
The processing method of tail gas during butane cis-butenedioic anhydride Download PDFInfo
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- CN109200772A CN109200772A CN201710521937.7A CN201710521937A CN109200772A CN 109200772 A CN109200772 A CN 109200772A CN 201710521937 A CN201710521937 A CN 201710521937A CN 109200772 A CN109200772 A CN 109200772A
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- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 title claims abstract description 56
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000001273 butane Substances 0.000 title claims abstract description 47
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000003672 processing method Methods 0.000 title claims abstract description 30
- 239000012528 membrane Substances 0.000 claims abstract description 81
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- 229920002301 cellulose acetate Polymers 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims description 106
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 60
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 34
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 32
- 235000019441 ethanol Nutrition 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 229910001868 water Inorganic materials 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 235000019260 propionic acid Nutrition 0.000 claims description 16
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 230000008595 infiltration Effects 0.000 claims description 15
- 238000001764 infiltration Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 9
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 9
- 239000000428 dust Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 66
- 239000012535 impurity Substances 0.000 abstract description 14
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000007654 immersion Methods 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 description 31
- 238000007254 oxidation reaction Methods 0.000 description 31
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 30
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 239000002994 raw material Substances 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 11
- 238000000926 separation method Methods 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 8
- 238000004064 recycling Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 238000003860 storage Methods 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 5
- 235000013399 edible fruits Nutrition 0.000 description 5
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000012466 permeate Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229920006337 unsaturated polyester resin Polymers 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000006392 deoxygenation reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000005909 ethyl alcohol group Chemical group 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- 241001292396 Cirrhitidae Species 0.000 description 1
- 101150096408 P2OX gene Proteins 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- -1 V-V ion Chemical class 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 230000036244 malformation Effects 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/26—Drying gases or vapours
- B01D53/268—Drying gases or vapours by diffusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/704—Solvents not covered by groups B01D2257/702 - B01D2257/7027
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/80—Water
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The processing method of tail gas during butane cis-butenedioic anhydride separates tail gas by membrane reactor, and the film in membrane reactor is cellulose acetate film, and membrane aperture is 0.01um~1.0um, and internal diameter is 0.05mm~0.8mm, and wall thickness is 0.2mm~1.0mm；In the immersion treatment using the preceding aqueous solution by low-carbon alcohols 12h~for 24 hours at 60 DEG C~200 DEG C.The membrane reactor of specially treated is utilized in exhaust gas treating method of the invention, eliminate the molecular weight polymers impurity in membrane module, keep membrane module pore-size distribution more uniform, active principle and impurity in tail gas can be efficiently separated, is more advantageous to the enrichment for seeping butane-component in residual air；The present invention also has the advantages that equipment investment expense is low, service life is long, easy to operate, low energy consumption.
Description
Technical field
The present invention relates to a kind of processing methods of tail gas during butane oxidation cis-butenedioic anhydride.
Background technique
Maleic anhydride (cis-butenedioic anhydride, MA) also known as maleic anhydride are a kind of particularly important Organic Chemicals, consumption figure
It is only second to phthalic anhydride and aceticanhydride.Cis-butenedioic anhydride is very widely used, mainly for the production of unsaturated polyester resin (UPR), 1,4-butanediol
(BDO), the series such as coating resin, span polyimides, tetrahydrofuran (THF), gamma-butyrolacton, maleic acid and tetrahydro acid anhydrides essence
The raw material of thin chemicals and textile auxiliary, lube oil additive, medicine, food additives etc..Wherein, cis-butenedioic anhydride is maximum
Purposes be production UPR and BDO, account for about the 41.7% and 17.4% of total quantity consumed respectively.Cis-butenedioic anhydride 2012 annual output in China's reaches about
800kt increased 5 times than 2000.The nearly 400kt/a of production capacity will be increased newly to the end of the year 2014.
The production process route of cis-butenedioic anhydride can be divided into phthalic anhydride by-product method, benzene oxidatoin method, C by its raw material4Olefin oxidation method, just
4 kinds of butane oxidation method.The maleic anhydride yield of phthalic anhydride plant by-product is very limited, only accounts for the 5% of phthalic anhydride by-product yield, 60 years 20th century
Before generation, cis-butenedioic anhydride is produced through catalysis oxidation as raw material using benzene and is in the great majority.But since benzene catalytic oxidation technique generates sternly environment
Heavily contaminated, the utilization rate of benzene is low in addition and price is higher and higher, is ground with raw material cheap, that pollution is small to produce the technique of cis-butenedioic anhydride
Hair becomes hot spot concerned by people.
In the early 1960s, starting with the C of low cost4Fraction (mainly containing n-butene) is that raw material produces the new of cis-butenedioic anhydride
Technical study, but since certain embodiments belong to the endothermic reaction and by-product is more, cause technology development to delay.1974, beauty
On original benzene method process units, it is raw for raw material to use normal butane instead in succession for Monsanto company of state and Texas oil company
It produces cis-butenedioic anhydride and obtains success, then, U.S. Ha Kang (Halcon) company and scientific design technology (SD) company have developed jointly just
The new catalyst and production technology of butane oxidation cis-butenedioic anhydride so that preparing cis-anhydride by n-butane oxidation new technology obtain it is more rapid
Development.
The rate constant of the reaction of preparing cis-anhydride by n-butane oxidation is K=11.44 × 105exp (- 7180/T), studies have shown that
(VO) in the catalyst2P2O7A V atom and ligand hole on (020) crystal face of object phase, another V atom and offer alkene
The active O atom bonding of propyl forms (VO) since V2O2 and P2OX is combined2P2O7When, an O atom is lacked in structure and is caused
(VO)2P2O7(020) malformation of crystal face forces the position V-O to reverse or adjust bond strength, is formed by coordination chemistry
High activity V-V ion pair.V-V bond length is 0.333nm, exactly corresponds to C in normal butane1And C3Bond length between atom and H original,
To illustrate in catalyst (VO)2P2O7Effect of the object with respect to normal butane and V2O5-P2OXBetween interaction.
In butane oxidation cis-anhydride production process, the conversion ratio of normal butane about 82% is unreacted containing 18% in tail gas
Normal butane is said from angle of cutting down the consumption of raw materials is recycled, and unreacted normal butane should be isolated from tail gas, is recycled to reaction system
System recycles.But also containing carbon monoxide, acrylic acid, acetic acid, solvent etc., at belonging to, toxic, burn into is inflammable in tail gas
Explosive medium.If tail gas is not handled well, into blower inlet, it is recycled, is situated between in tail gas containing water, acid etc.
Matter, it will the leaf of the air blower equipment such as fall are caused to corrode, drastically influence the operational safety of device.
In butane oxidation maleic anhydride production, the method for tail gas separation recycling normal butane has absorption process, condensation method and absorption
Method etc.: 1) absorption process: absorption process is that the characteristic of special solvent (or solution of addition chemical agent) is dissolved in using a certain tail gas
A kind of method handled；2) condensation method: condenser can be made it through for high-content tail gas, available gas is dropped
As low as boiling point hereinafter, condensing into liquid with recycling and reusing；3) absorption method: absorption method is that have using certain from gas phase mixture
In adsorb the porous solid (adsorbent) of certain component abilities selectively to remove a kind of method of impurity in tail gas.At present
To handle the active charcoal of the most common adsorbent of impurity in tail gas and activated carbon fibre, device used is valve transfer formula two
Bed (or more) absorber.
" chemical industry and engineering technology " the 4th phase of volume 23 in 2006 reports n butane oxidation production cis-butenedioic anhydride vent gas treatment
Technology, with the tail gas of flame combustion formula oxidator method processing butane oxidation cis-butenedioic anhydride, main body is incinerator, including burning
Device, mixing section, burning zone and exhaust section generate steam equipped with waste heat boiler recycling heat.Such method is to butane oxidation system
A kind of processing method of cis-butenedioic anhydride tail gas, and do not achieve the purpose that recycling.
" petrochemical technology and application " the 1st phase of volume 32 in 2014 reports n butane oxidation method maleic anhydride production work
Skill tail gas recycles, and the principle of exhaust gas circulation process is by processes such as cooling, separation, washings by reactive absorption tower tail gas
The impurity such as solvent, acrylic acid, acetic acid, the water of middle entrainment separation, to recycle the complete normal butane of wherein unreacted.The method work
Skill process complexity and high production cost, in addition can generate a large amount of scrub raffinate, pollute environment.
To sum up, the generally existing complex technical process of method in the prior art and the shortcomings that high production cost, and butane is pure
Rate is low, in the prior art without using film come the technical solution of separating treatment butane oxidation cis-butenedioic anhydride tail gas.
Summary of the invention
To solve butane oxidation cis-butenedioic anhydride tail gas in the prior art, there are complex treatment process, at high cost and vent gas treatment effect
Fruit problem not up to standard, the present invention is quasi- to provide a kind of processing method of butane oxidation cis-butenedioic anhydride tail gas, with limited means process film
Component simultaneously controls operating condition to tail gas progress separating treatment, and the isolated higher butane-component of purity can direct circulation benefit
With.
To realize the above-mentioned technical purpose, the present invention uses following technological means:
The present invention provides a kind of processing methods of tail gas during butane cis-butenedioic anhydride, comprising the following steps: removes tail gas dehydration
UF membrane, the operating condition of UF membrane are carried out by membrane reactor after dirt are as follows: pressure 0.2MPa~2.0MPa, temperature 60 C~
120 DEG C, intake velocity 1.0m/s~5.0m/s, obtain rich in carbon monoxide, propionic acid, acetic acid, solvent, vapor infiltration gas and
Infiltration residual air rich in butagas, nitrogen；
Wherein, the film in the membrane reactor is cellulose acetate film, and membrane aperture is 0.01um~1.0um, internal diameter 0.05mm
~0.8mm, wall thickness are 0.2mm~1.0mm；
The membrane reactor is handled in the following manner using preceding:
First remove the oxygen in low-carbon alcohols and deionized water, by the aqueous solution that membrane module is soaked in low-carbon alcohols be placed in closed container in
12h~for 24 hours is handled at 60 DEG C~200 DEG C；The low-carbon alcohols are at least one of the alcohol of C1 ~ C4.
In above-mentioned processing method, it will be apparent to a skilled person that in the butane oxidation cis-butenedioic anhydride tail gas
Containing the complete butylene of unreacted, recoverable carries out reproduction, but wherein also containing water, carbon monoxide, nitrogen, oxygen,
The impurity such as carbon dioxide, acetic acid, propionic acid, cis-butenedioic anhydride, each component content is different because of respective process distinction in tail gas, to make
Those skilled in the art are more fully understood by the present invention, and processing method of the present invention is particularly suitable for following impurity content
Exhaust gas treating method: by weight, water content 1.0%-5.5%, carbon monoxide content 0.5%-6.5%, nitrogen content is
65.0%-80.0%, oxygen content 5.0%-25.0%, carbon dioxide content 0.1%-5.5%, acetic acid content 0.005%-
0.15%, propionic acid content 0.005%-0.15%, cis-butenedioic anhydride content are 0.002%-0.1%, and surplus is butane.Wherein preferred group
Cheng Shi: by weight, water content 1.5%-3.0%, carbon monoxide content 0.5%-4.5%, nitrogen content 65.0%-
70.0%, oxygen content 5.0%-15.0%, carbon dioxide content 0.5%-3.5%, acetic acid content 0.005%-0.01%, third
Acid content is 0.005%-0.10%, and cis-butenedioic anhydride content is 0.002%-0.08%, and surplus is butane.And it should be strongly noted that on
The tail gas for stating composition is handled using method of the invention, available more preferably separating resulting, the gas after making separation
Middle butane content meets the requirement as feedstock circulation reproduction, and impurity therein is substantially achieved removal, it is anti-to will not influence technique
It answers, and is not to say that the tail gas except this composition and is unsuitable for being handled with the method.
In above-mentioned processing method, the dehydration dedusting is to remove all diameters the consolidating greater than 0.01 μm carried secretly in tail gas
Body particle, water mist and aerosol, micronic dust content≤0.01mg/Nm in the tail gas that makes that treated3, water content≤5PPm.Processing side
Method is known to the skilled person, such as inertial dust collection method, wet dedusting method, Cottrell process, filtering type process of cleaning, monotubular rotation
Wind process of cleaning, multi-cyclone process of cleaning, centrifugal force separate, gravitational settling, baffling separation, silk screen separation, ultra-filtration and separation and filler
Separation etc., preferably centrifugal force separate, filtering type process of cleaning.
In above-mentioned processing method, tail gas can make tail by Pneumatic booster pump or gas-booster before being passed through membrane separator
Gas is pressurized to required pressure；Exhaust temperature is set to be down to required temperature by heat exchange mode, heat exchange mode includes various hybrid, storages
Hot type or dividing wall type heat exchanger, preferably dividing wall type heat exchanger, wherein dividing wall type heat exchanger can be jacket type, tubular type, it is board-like or
The custom design heat exchanger of various abnormal shape heat-transfer area compositions；The type of flow of the cold fluid and hot fluid in heat exchanger include fair current, adverse current,
Hand over stream, mixed flow again, preferably adverse current.
In above-mentioned processing method, as a further preference, the operating condition of the UF membrane are as follows: pressure 0.5MPa~
1.0MPa, temperature 60 C~100 DEG C, intake velocity are 1.0m/s~3.0m/s.
In above-mentioned processing method, as a further preference, the membrane aperture of the cellulose acetate film be 0.01um~
0.08um, internal diameter are 0.05mm~0.5mm, and wall thickness is 0.2mm~0.8mm, and more preferably membrane aperture is 0.01um~0.5um,
Internal diameter is 0.05mm~0.1mm, and wall thickness is 0.5mm~0.7mm.
In above-mentioned processing method, as a further preference, the low-carbon alcohols are selected from methanol, ethyl alcohol, propyl alcohol, isopropyl
At least one of alcohol, n-butanol, the tert-butyl alcohol, sec-butyl alcohol and isobutanol；Preferably propyl alcohol, isopropanol, n-butanol, the tert-butyl alcohol,
At least one of sec-butyl alcohol and isobutanol.
In above-mentioned processing method, in the aqueous solution of the low-carbon alcohols volumetric concentration of alcohol be 0.5% ~ 20%, preferably 1% ~
10%。
It should be strongly noted that membrane module, in the process of processing, used solution has to pass through deoxygenation
Processing additionally should ensure that in treatment fluid without containing mechanical dust.
In above-mentioned processing method, as a further preference, using low-carbon alcohols aqueous solution soaking temperature be 80 DEG C-
150 DEG C, more preferably 100 DEG C ~ 150 DEG C, soaking time is preferably 12 ~ 18h.
When handling membrane module, using closed container, for all kinds of inert material linings suitable for hydro-thermal reaction
Reactor, such as the container of enamel, glass, ceramics or tetrafluoroethene lining.
In above-mentioned processing method, immersion of the present invention is subject to liquid and there completely was not membrane module.
In above-mentioned processing method, the membrane reactor includes shell and membrane module, and membrane module is arranged in shell, in shell
One end of body and membrane module are equipped with gas inlet parallel, are equipped with parallel in the other end and membrane module of shell and seep residual air outlet, shell
Body side surface, which is equipped with, seeps vent outlet.
After above-mentioned vent gas treatment, obtain rich in carbon monoxide, propionic acid, acetic acid, solvent, vapor infiltration gas and
Infiltration residual air rich in butagas, nitrogen seeps residual air and returns to the butane oxidation stage as raw material, and permeating gas can further recycle respectively
Component.
Compared with prior art, butane oxidation cis-butenedioic anhydride exhaust gas treating method of the invention has the advantage that
1. the present invention is impregnated membrane reactor with toluene and methyl iso-butyl ketone (MIBK) under given conditions, is carried out stage by stage with water
The mode of processing eliminates the molecular weight polymers impurity in membrane module, keeps membrane module pore-size distribution more uniform, be more advantageous to
Seep the enrichment of butane-component in residual air.
2. butane oxidation cis-butenedioic anhydride exhaust gas treating method of the invention has equipment investment expense compared with other techniques
Low, the advantages of service life is long, easy to operate, low energy consumption；Membrane reactor gas separation selectivity after specially treated is good,
Separative efficiency is high, effectively excludes impurity acetic acid, propionic acid, cis-butenedioic anhydride and the moisture in tail gas, active principle butane contains in tail gas
Amount is promoted to 1.60% or more by 1.1, fully meets the requirement that direct circulation is used as raw material, and entire technique does not produce
Raw secondary pollution.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The concrete technology flow process figure of butane oxidation cis-butenedioic anhydride tail gas is handled used in Fig. 1 embodiment；
The structural schematic diagram of Fig. 2 membrane reactor；
Wherein 1. gas centrifuge, 2. gas-boosters I, 3. high pressure storage tanks, 4. active carbon filters, 5. contra-flow heat exchangers, 6.
Accurate filter, 7. membrane reactors, 8. gas-boosters II, 9. gas inlets, 10. seep vent outlet, 11. membrane modules, 12. shells
Body, 13. seep residual air outlet, 14. pipelines I, 15. pipelines II, 16. pipelines III.
Specific embodiment
Following non-limiting embodiments can with a person of ordinary skill in the art will more fully understand the present invention, but not with
Any mode limits the present invention.
In the examples below, be all made of technological process device shown in FIG. 1 to butane oxidation cis-butenedioic anhydride tail gas at
Reason, the room temperature tail gas from butane oxidation technique first passes through gas centrifuge 1, it is preliminary remove the solid particle carried in tail gas and
Water, then 0.5MPa~1.0Mpa is pressurized to by gas-booster I 2, it is further through active carbon filter 4 into high pressure storage tank 3
It is dehydrated dedusting, then makes exhaust temperature up to 50 DEG C~80 DEG C after the heat exchange of counter-current pipe exchanger 5, again through accurate filter 6
Micronic dust content≤0.01mg/Nm is obtained after removing solid particle of all diameters greater than 0.01 μm3, water content≤3PPm enters film
It is anti-to enter film under conditions of pressure 0.5MPa~1.0MPa, temperature 50 C~80 DEG C, intake velocity 0.5m/s~3.0m/s for gas
Device 7 is answered, purified infiltration residual air is isolated and concentrates the infiltration gas of impurity.Residual air is wherein seeped from residual air outlet is seeped through pipeline II
15 draw return butane oxidation device, and partial penetration gas returns to activity by gas-booster II 8 and pipeline III 16 through pipeline I 14
Carbon filter 4, another part permeate the recycling that gas carries out acrylic acid, acetic acid, solvent.
Fig. 2 is membrane reactor structural schematic diagram used in the embodiment of the present invention.Membrane reactor has shell 12, in shell
Equipped with membrane module 11, it is equipped with gas inlet 9 parallel in one end of shell 12 and membrane module 11, in the other end and film group of shell 12
Part 11 is equipped with parallel seeps residual air outlet 13, and housing side, which is equipped with, seeps vent outlet 10.Tail gas is in membrane module internal flow, as slow
The butane-component of gas walks membrane module tube side and is seeped 13 discharge of residual air outlet, and the impurity gas as fast gas appears membrane module through permeating gas
10 discharge of outlet.The material that the membrane module uses is cellulose acetate film.
Film parameters used in embodiment are shown in Table 1, and the volume composition of used butane oxidation device exhaust is listed in table
2。
Table 1
Table 2
% in following embodiment is weight percentage unless otherwise specified.
Embodiment 1
Using butane oxidation device exhaust listed by table 2 as raw material, the solid carried in tail gas is tentatively removed through gas centrifuge 1
After grain and water, enter high pressure storage tank 3 after being pressurized to 0.8MPa by gas-booster I 2；It is further taken off through active carbon filter 4
Water dedusting, micronic dust content is 0.001mg/Nm in treated tail gas3, water content 2PPm, then through counter-current pipe exchanger 5
Make exhaust temperature up to 80 DEG C after heat exchange, membrane reactor 7, separation are entered under conditions of pressure 0.8MPa, intake velocity 1.0m/s
Infiltration residual air rich in butane and the infiltration gas containing acetic acid, propionic acid, cis-butenedioic anhydride and moisture out.It seeps residual air and is sent into butane oxidation device work
For the raw material for synthesizing cis-butenedioic anhydride；Gas is permeated after different adsorbents adsorb laggard one-step removal butane therein as backflow gas pressurization
Membrane separator 7 is returned to continue to purify；Another part permeates the recycling that gas carries out acetic acid, propionic acid, cis-butenedioic anhydride.Residual air composition result is seeped to see
Table 3.
Embodiment 2
According to the method for embodiment 1, high pressure storage tank 3 will be only entered after gas boosting to 1.0MPa；Through active carbon filter 4 into
One step is dehydrated dedusting, and micronic dust Content is 0.001mg/Nm in treated tail gas3, water content 1.5PPm countercurrently changed
Hot device 5 makes exhaust temperature up to 80 DEG C after exchanging heat, and membrane reactor 7 is entered under conditions of pressure 0.5MPa, intake velocity 0.5m/s,
Isolate the infiltration residual air rich in butane and the infiltration gas containing acetic acid, propionic acid, cis-butenedioic anhydride and moisture.It seeps residual air and is sent into butane oxidation dress
Set the raw material as synthesis cis-butenedioic anhydride；Infiltration gas adsorbs laggard one-step removal butane therein as backflow gas through different adsorbents and adds
Membrane separator 7 is returned after pressure to continue to purify；Another part permeates the recycling that gas carries out acetic acid, propionic acid, cis-butenedioic anhydride.Seep residual air composition knot
Fruit is shown in Table 3.
Embodiment 3
According to the method for embodiment 1, high pressure storage tank 3 will be only entered after gas boosting to 1.0MPa；Make through active carbon filter 4
Obtaining micronic dust content in tail gas is 0.001mg/Nm3, water content is that 5PPm enters film gas, makes tail gas after the heat exchange of contra-flow heat exchanger 5
Temperature enters membrane reactor 7 under conditions of pressure 1.0MPa, intake velocity 3.0m/s, isolates rich in butane up to 80 DEG C
Seep residual air and the infiltration gas containing acetic acid, propionic acid, cis-butenedioic anhydride and moisture.It seeps residual air and is sent into butane oxidation device as synthesis cis-butenedioic anhydride
Raw material；Infiltration gas returns to membrane separator after different adsorbents adsorb laggard one-step removal butane therein as backflow gas pressurization
7 continue to purify；Another part permeates the recycling that gas carries out acetic acid, propionic acid, cis-butenedioic anhydride.Seeping residual air composition the results are shown in Table 3.
Embodiment 4
Membrane module 11 is carried out the following processing: isopropanol, sec-butyl alcohol and deionized water being subjected to deoxygenation processing in advance first, is prepared
Isopropanol and sec-butyl alcohol volume fraction are 5% low-carbon mixed alkoxide solution, and membrane module 11 is placed in above-mentioned low-carbon mixed alkoxide solution
In, it is put into closed container, is warming up to 100 DEG C, immersion treatment 12h.
According to method identical with 1 condition of embodiment, with treated above, membrane module 11 is used for vent gas treatment.Seep residual air
Composition the results are shown in Table 3.
Embodiment 5
According to the processing method of membrane module in embodiment 4, isopropanol and sec-butyl alcohol are only replaced with ethyl alcohol and sec-butyl alcohol, other
Part is same as Example 4, handles membrane module.
According to method identical with 2 condition of embodiment, with treated above, membrane module 11 is used for vent gas treatment.Seep residual air
Composition the results are shown in Table 3.
Embodiment 6
According to the processing method of membrane module in embodiment 4, isopropanol and sec-butyl alcohol are only replaced with ethyl alcohol and isopropanol, other
Part is same as Example 4, handles membrane module.
According to method identical with 3 condition of embodiment, with treated above, membrane module 11 is used for vent gas treatment.Seep residual air
Composition the results are shown in Table 3.
Embodiment 7
According to the method for embodiment 4, isopropanol and sec-butyl alcohol are only replaced with sec-butyl alcohol, other conditions are same as Example 4, right
Membrane module is handled；And membrane module 11 is used for vent gas treatment with treated, seeping residual air composition the results are shown in Table 3.
Embodiment 8
According to the method for embodiment 4, isopropanol and sec-butyl alcohol are only replaced with isopropanol, other conditions are same as Example 4, right
Membrane module is handled；And membrane module 11 is used for vent gas treatment with treated, seeping residual air composition the results are shown in Table 3.
Embodiment 9
According to the method for embodiment 4, isopropanol and sec-butyl alcohol, other conditions and embodiment 4 are only replaced with methanol and isopropanol
It is identical, membrane module is handled；And membrane module 11 is used for vent gas treatment with treated, seeping residual air composition the results are shown in Table 3.
Embodiment 10
According to the method for embodiment 4, isopropanol and sec-butyl alcohol, other conditions and embodiment 4 are only replaced with methanol and sec-butyl alcohol
It is identical, membrane module is handled；And membrane module 11 is used for vent gas treatment with treated, seeping residual air composition the results are shown in Table 3.
Embodiment 11
According to the method for embodiment 4, low-carbon mixed alkoxide solution is only replaced with 5% methanol, other conditions are same as Example 4, right
Membrane module is handled；And membrane module 11 is used for vent gas treatment with treated, seeping residual air composition the results are shown in Table 3.
Embodiment 12
According to the method for embodiment 4, the concentration of isopropanol and sec-butyl alcohol is only changed into 0.5% and 9.5%, other conditions respectively
It is same as Example 4, membrane module is handled；And with treated, membrane module 11 is used for vent gas treatment, seeps residual air composition knot
Fruit is shown in Table 3.
Embodiment 13
According to the method for embodiment 4, the concentration of isopropanol and sec-butyl alcohol is only changed into 9.5% and 0.5%, other conditions respectively
It is same as Example 4, membrane module is handled；And with treated, membrane module 11 is used for vent gas treatment, seeps residual air composition knot
Fruit is shown in Table 3.
Embodiment 14
According to the method for embodiment 4, the concentration of isopropanol and sec-butyl alcohol is only changed into 0.5% and 0.5%, other conditions respectively
It is same as Example 4, membrane module is handled；And with treated, membrane module 11 is used for vent gas treatment, seeps residual air composition knot
Fruit is shown in Table 3.
From table 3 it can be seen that butane oxidation device exhaust is after not pretreated membrane separator purification, it is effective in tail gas
Component butane content still contains the impurity such as a small amount of acetic acid, propionic acid and cis-butenedioic anhydride 1.1% or so, and passes through pretreated film
After separator purification, impurity acetic acid, propionic acid, cis-butenedioic anhydride and moisture in tail gas have obtained effective exclusion, active principle in tail gas
Butane content is 1.60% or more, can be used as the raw material of synthesis cis-butenedioic anhydride workshop section completely, has reached the requirement being recycled.
Table 3.
Claims (10)
1. the processing method of tail gas during butane cis-butenedioic anhydride, comprising the following steps: pass through film reaction after tail gas is dehydrated dedusting
Device carries out UF membrane, the operating condition of UF membrane are as follows: pressure 0.2MPa~2.0MPa, temperature 60 C~120 DEG C, intake velocity
1.0m/s~5.0m/s is obtained rich in carbon monoxide, propionic acid, acetic acid, solvent, the infiltration gas of vapor and rich in butagas, nitrogen
The infiltration residual air of gas；
Wherein, the film in the membrane reactor is cellulose acetate film, and membrane aperture is 0.01um~1.0um, internal diameter 0.05mm
~0.8mm, wall thickness are 0.2mm~1.0mm；
The membrane reactor is handled in the following manner using preceding:
First remove the oxygen in low-carbon alcohols and deionized water, by the aqueous solution that membrane module is soaked in low-carbon alcohols be placed in closed container in
12h~for 24 hours is handled at 60 DEG C~200 DEG C；The low-carbon alcohols are at least one of the alcohol of C1 ~ C4.
2. processing method according to claim 1, which is characterized in that the operating condition of the UF membrane are as follows: pressure
0.5MPa~1.0MPa, temperature 60 C~100 DEG C, intake velocity are 1.0m/s~3.0m/s.
3. processing method according to claim 1, which is characterized in that the low-carbon alcohols are selected from methanol, ethyl alcohol, propyl alcohol, different
At least one of propyl alcohol, n-butanol, the tert-butyl alcohol, sec-butyl alcohol and isobutanol.
4. processing method according to claim 3, which is characterized in that the volumetric concentration of alcohol in the aqueous solution of the low-carbon alcohols
It is 0.5% ~ 20%.
5. processing method according to claim 3 or 4, which is characterized in that be using the temperature that low carbon alcohol solution impregnates
80℃-150℃。
6. processing method according to claim 1, which is characterized in that the membrane aperture of the cellulose acetate film is 0.01um
~0.08um, internal diameter are 0.05mm~0.5mm, and wall thickness is 0.2mm~0.8mm.
7. processing method according to claim 6, which is characterized in that the membrane aperture of the cellulose acetate film is 0.01um
~0.5um, internal diameter are 0.05mm~0.1mm, and wall thickness is 0.5mm~0.7mm.
8. processing method according to claim 1, which is characterized in that micronic dust in the dehydration dedusting makes that treated tail gas
Content≤0.01mg/Nm3, water content≤5PPm.
9. processing method according to claim 1, which is characterized in that the composition of the tail gas are as follows: by weight, water content
For 1.0%-5.5%, carbon monoxide content 0.5%-6.5%, nitrogen content 65.0%-80.0%, oxygen content 5.0%-
25.0%, carbon dioxide content 0.1%-5.5%, acetic acid content 0.005%-0.15%, propionic acid content 0.005%-0.15%,
Cis-butenedioic anhydride content is 0.002%-0.1%, and surplus is butane.
10. processing method according to claim 9, which is characterized in that the composition of the tail gas are as follows: by weight, water contains
Amount is 1.5%-3.0%, carbon monoxide content 0.5%-4.5%, nitrogen content 65.0%-70.0%, oxygen content 5.0%-
15.0%, carbon dioxide content 0.5%-3.5%, acetic acid content 0.005%-0.01%, propionic acid content 0.005%-0.10%,
Cis-butenedioic anhydride content is 0.002%-0.08%, and surplus is butane.
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| CN106669376A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Method for using butane oxidation tail gas |
| CN106731890A (en) * | 2016-12-26 | 2017-05-31 | 华北电力大学 | A kind of inoranic membrane and preparation method for trapping vapor in coal steam-electric plant smoke |
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| US4606740A (en) * | 1985-04-15 | 1986-08-19 | Uop Inc. | Separation of polar gases from nonpolar gases |
| CN1438068A (en) * | 2003-03-20 | 2003-08-27 | 临海市越丰化工厂 | Method for pretreating large-hole adsorption resin |
| CN102753255A (en) * | 2010-02-25 | 2012-10-24 | 株式会社神钢环境舒立净 | Separation membrane modification method and separation membrane modification device |
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Effective date of registration: 20231013 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |